发光铱(Ⅲ)配合物抗肿瘤活性研究及应用

铱(Ⅲ)配合物因其发光量子产率高且波长易调控、发光寿命长和光稳定性好的特点,在发光材料领域备受关注。铱(Ⅲ)配合物细胞渗透能力强,能靶向多种细胞组织并影响其结构和功能,表现出独特的抗肿瘤活性,是目前金属抗肿瘤药物特别是PDT光敏剂方向的研究热点。本文重点关注铱(Ⅲ)配合物的结构对其发光性能与抗肿瘤性能的影响,综述了近期铱(Ⅲ)配合物在生物成像、探针与传感、抗肿瘤诊疗等领域的研究进展,并对目前研究中存在的问题及其应用前景进行探讨和展望。     

Excited-State Dynamics of Non-Luminescent and Luminescent π-Radicals

Recently, the potential use of organic π-radicals and related spin systems has been expanded to modern technological applications. The unique excited-state dynamics of organic π-radicals can be useful to improve the stability of photochemically unstable organic compounds, make the polarization transfer applicable to information technology, and achieve effective up-conversion of interest for luminescence bioimaging, among others. Furthermore, highly luminescent stable π-radicals have been recently reported, which are especially interesting for application in organic light-emitting devices owing to their potential to provide an internal quantum efficiency of 100 %. Thus, the excited-state nature of stable π-radicals as well as the control of their excited-state spin dynamics are emerging topics both in terms of fundamental science and related technological applications. In this minireview, we focus on the excited-state dynamics of both photostable non(weakly)-luminescent and luminescent π-radicals, which are opposites of each other. In particular, we cover the following topics: 1) effective generation of high-spin photoexcited states and control of the excited-state dynamics by using non-luminescent π-radicals, 2) unique excited-state dynamics of luminescent π-radicals and radical excimers, and 3) applications utilizing excited-state dynamics of π-radicals.     

A stable pillared metal–organic framework constructed by H4TCPP ligand as luminescent sensor for selective detection of TNP and Fe3+ ions

A novel luminescent metal–organic framework ( Zn‐TCPP/BPY ) with pillared structure based on 2,3,5,6‐tetrakis(4‐carboxyphenyl)pyrazine (H₄TCPP) and 4,4′‐bipyridine (BPY) has been designed and synthesized through a solvothermal reaction. The [Zn₂(COO)₄] paddlewheel units are linked by TCPP^4? ligands to form two‐dimensional layers and further connected by BPY ligands as pillars to construct the twofold interpenetrating three‐dimensional framework. Interestingly, Zn‐TCPP/BPY possesses outstanding stability in organic solvents and water as well as maintains its structural rigidity in aqueous solutions of different pH values (3–12). After activation, Zn‐TCPP/BPY possesses permanent porosity with Brunauer–Emmett–Teller surface area of 630 m² g^–1. Remarkably, Zn‐TCPP/BPY displays excellent fluorescent property in virtue of the aggregation‐induced emission effect of the H₄TCPP ligand, which can be highly active and quenched by small amounts of 2,4,6‐trinitrophenol (TNP) and Fe³⁺ ions. Furthermore, the detection effect of Zn‐TCPP/BPY remains basically the same even after five cycles. The excellent stability, high sensitivity, and recyclability of Zn‐TCPP/BPY make it an outstanding chemical sensor for detecting TNP and Fe³⁺ ions.     

Luminescent Thin Films Enabled by CsPbX3 (X=Cl,Br, I) Precursor Solution

Inorganic cesium lead halide perovskite nanocrystals are candidates for lighting and display materials due to their outstanding optoelectronic properties. However, the dissolution issue of perovskite nanocrystals in polar solvents remains a challenge for practical applications. Herein, we present a newly designed one-step spin-coating strategy to prepare a novel multicolor-tunable CsPbX₃ (X=Cl, Br, I) nanocrystal film, where the CsPbX₃ precursor solution was formed by dissolving PbO, Cs₂CO₃, and CH₃NH₃X into the ionic liquid n-butylammonium butyrate. The as-designed CsPbX₃ nanocrystal films show high color purity with a narrow emission width. Also, the blue CsPb(Cl/Br)₃ film demonstrates an absolute photoluminescence quantum yields (PLQY) of 15.6 %, which is higher than 11.7 % of green CsPbBr₃ and 8.3 % of red CsPb(Br/I)₃ film. This study develops an effective approach to preparing CsPbX₃ nanocrystal thin films, opening a new avenue to design perovskite nanocrystals-based devices for lighting and display applications.     

(Gd,Lu)3Al5O12∶Tb3+,Eu3+透明陶瓷制备与发光性能

通过简单的化学沉淀法制备了纳米前驱体,结合真空烧结工艺,制备了一系列镥稳定钆铝石榴石{(Gd, Lu)₃Al₅O₁₂∶Tb,Eu}透明陶瓷。将透明陶瓷加工成1 mm厚的圆片,对透明陶瓷样品进行了X射线衍射、光致发光、透过率和衰减时间等表征。高温烧结过后,陶瓷样品仍保持稳定的石榴石相。选定313 nm作为透明陶瓷的激发波长,可获得最强的荧光发射。此外,通过对不同样品进行紫外可见荧光测试,获得了由绿光到红光的可调节发射。在313 nm激发,543 nm和591 nm的监测波长下,透明陶瓷样品均具有Eu³⁺的毫秒级衰减时间。     

用于液体激光介质的Nd~(3+)离子掺杂氟化镧纳米颗粒的制备与性能表征

设计并合成了掺杂不同Nd3+离子浓度的氟化镧纳米颗粒,并用油酸进行了表面修饰,使得这类纳米颗粒可分散于常见的有机溶剂中形成透明、均一、稳定的溶液。对纳米颗粒的结构、晶相以及发光性能进行了表征。固体和溶液材料在1 060 nm都有强的发射峰,说明纳米晶格可有效地保护Nd3+离子免受外界环境对发光的猝灭影响。纳米颗粒有机溶液的吸收损耗和散射损耗测试结果表明,其总损耗系数能够满足激光介质材料的损耗要求,为该材料的实用化打下了基础。     

New glass ceramics: an effective conjunction of wet chemistry synthesis and sintering

A glass with CdS nanoparticles was used simultaneously as a matrix for Ce-doped garnet and a yellow-red phosphor to prepare luminescent glass ceramics for the sources of white light. CdS nanoparticles compensate for the unbalanced Ce³⁺ emission spectrum of the composite material due to the addition of a red component. The synthesized composite material can be a tunable light converter due to altered luminescence spectra by changing the sintering conditions and excitation wavelength     

Facile Formation of Sulfurized Nanorod-Like ZnO/Zn(OH)2 and Hierarchical Flower-Like γ-Zn(OH)2/ϵ-Zn(OH)2 from a Green Synthesis and Application as Luminescent Solar Concentrator

This research endeavors to overcome the significant challenge of developing materials that simultaneously possess photostability and photosensitivity to UV-visible irradiation. Sulfurized nanorod (NR)-like ZnO/Zn(OH)₂ and hierarchical flower-like γ-Zn(OH)₂/ϵ-Zn(OH)₂ were identified from XRD diffraction patterns and Raman vibrational modes. The sulfurized material, observed by FEG-SEM and TEM, showed diameters ranging from 10 and 40 nm and lengths exceeding 200 nm. The S²⁻ ions intercalated Zn²⁺, modulating NRs to dumbbell-like microrods. SAED and HRTEM illustrated the atomic structure in (101) crystal plane. Its direct band gap of 3.0 eV was attributed to the oxygen vacancies, which also contribute to the deep-level emissions at 422 and 485 nm. BET indicated specific surface area of 4.4 m² g⁻¹ and pore size as mesoporosity, which are higher compared to the non-sulfurized analogue. These findings were consistent with the observed photocurrent, photostability and photoluminescence (PL), further supporting the suitability of sulfurized NR-like ZnO/Zn(OH)₂ as a promising candidate for Luminescent solar concentrators (LSC)-photovoltaic (PV) system.     

Combined DFT and wave function theory approach to excited states of lanthanide luminescent materials: A case study of LaF3:Ce3+

Lanthanide luminescent materials play key roles in modern society, but their first-principles treatment remains a great challenge due to complex manifold of electronic excited states and the difficulty in performing excited state structural relaxations that is necessary to model luminescent properties. Herein, we propose a practical approach that combines embedded cluster model (ECM) based multi-configurational wave function theory (WFT) and occupancy constrained density-functional theory plus the Hubbard U correction (OC-DFT + U) to treat lanthanide doped luminescent materials, using LaF₃:Ce³⁺, a typical scintillator with low symmetry, as a case study. We show that the combined approach yields accurate absorption energies with an error on the order of 200 cm⁻¹, but the emission energies are significantly underestimated, the origin of which is further clarified by vibrationally resolved absorption and emission spectra calculation. This work demonstrates the possibility of combining ECM-based wave function theory and periodic DFT into a comprehensive computational scheme for lanthanide luminescent materials and highlights the limitations of the current implementation of OC-DFT + U for excited state structural optimization.